Novel basic pyrazoline dyes

ABSTRACT

BASIC DYESTUFFS OF THE GENERAL FORMULA   (1-((-A-N(-R8)=(C(-R5)-C(-R6))N=)&gt;C-C(-R7)=CH-),3-(R-   (CH=CH)M-),4-R1,4-R2,5-R3,5-R4-PYRAZOLIDINE)(+) X(-)   IN WHICH A DENOTES THE RESIDUAL MEMBERS OF A HETEROCYCLIC 5- OR 6-RING WITH WHICH FURTHER RINGS MAY BE FUSED; R MEANS AN ARYL RADICAL OR A HETEROCYCLIC RADICAL OF AROMATIC CHARACTER; R1, R2, R3, R4, R5, AND R6, INDEPENDENTLY OF ONE ANOTHER, DENOTE HYDROGEN OR A NON-IONIC RADICAL, PERFERABLY ALKYL, CYCLOALKYL, ARALKYL, OR ARYL RADICALS, AND R1 MAY BE LINKED TO R2 OR R3 OR R; R7 MEANS HYDROGEN OR A NITRILE GROUP; R8 IS AN ALKYL, CYCLOALKYL, ARALKYL OR ARYL RADICAL, AND R8 MAY ALSO BE LINKED TO ANY RING FUSED WITH A; X(-) MEANS AN ANION; AND M AND N, INDEPENDENTLY OF ONE ANOTHER DENOTE THE NUMBERS 0 OR 1; AND IN WHICH THE CARBOCYCLIC AND HETEROCYCLIC RADICALS AND THE ACYCLIC HYDROCARBON RADICALS CONTAINED IN THESEFORMULAE MAY CARRY NONIONIC SUBSTITUENTS, AS WELL AS PROCESSES FOR THE PRODUCTION THEREOF, AND THEIR USE FOR DYEING AND PRINTING.

United States Patent NOVEL BASIC PYRAZOLINE DYES Alfred Brack, Leverkusen, Germany, assignor to Bayer Aktiengesellschaft, Leverkusen, Germany No Drawing. Filed Aug. 31, 1970, Ser. No. 68,485 Claims priority, application Germany, Sept. 5, 1969, P 19 45 053.4; July 23, 1970, P 20 36 505.3 Int. Cl. C09b 23/00 US. Cl. 260240.8 9 Claims ABSTRACT OF THE DISCLOSURE Basic dyestuffs of the general formula in which A denotes the residual members of a heterocyclic or 6-ring with which further rings may be fused; R means an aryl radical or a heterocyclic radical of aromatic character; R R R R R and R independently of one another, denote hydrogen or a non-ionic radical, preferably alkyl, cycloalkyl, aralkyl, or aryl radicals, and R may be linked to R or R or R; R means hydrogen or a nitrile group; R is an alkyl, cycloalkyl, aralkyl or aryl radical, and R may also be linked to any ring fused with A; X means an anion; and m and n, independently of one another denote the numbers 0 or 1; and in which the carbocyclic and heterocyclic radicals and the acyclic hydrocarbon radicals contained in these formulae may carry nonionic substituents, as well as processes for the production thereof, and their use for dyeing and printing.

The present invention relates to new basic dyes of the general formula in which A represents the radicals of a 5- or 6-member heterocyclic ring to which other rings can be fused, R is an aryl radical or an aromatic heterocyclic radical, R R R R R and R independently of each other being hydrogen or a non-ionic radical, advantageously alkyl, cycloalkyl, aralkyl or aryl radicals, R is hydrogen or a nitrile group and R is hydrogen, an alkyl, cycloalkyl, aralkyl or aryl radical, on the condition that if p indicates the number 1, R cannot stand for hydrogen, X is an anion and m, n and p independently represent thenumbers 0 or 1, and wherein the radicals R to R on the one hand and R R and R on the other can be interconnected with formation of one or more ring systems, and R can be connected to a ring fused on A, and wherein thecarbocyclic and heterocyclic rings and the acyclic radicals may contain the usual non-ionic substituents used in the chemistry of cationic dyes, as well as to the process of their manufacture and their use as materials for dyeing and printing of natural and synthetic materials.

Conventional non-ionic substituents that are suitable in 3,770,727 Patented Nov. 6, 1973 the chemistry of basic dyes are for example alkyl, hydroxy-, alkyloxy-, aryloxy, acyloxy, acyl, alkoxycarbonyl-, amidocarbonyl-, nitrile-, nitro-, amino-, acylamino-, alkylamino-, dialkylamino-, sulfonyl-, mercapto, alkylmercaptoand arylmercapto groups as well as halogen atoms such as fluorine, chlorine and bromine.

Suitable alkyl radicals are e.g. methyl, ethyl, n-propyl, isopropyl, n-butyl, iso-butyl, n-amyl, iso-amyl, neo-pentyl, allyl and their products of substitution such as beta cyanethyl, beta chloroethyl, beta methoxyethyl, beta ethoxyethyl, beta ethoxycarbonylethyl.

The cyclohexyl radical is especially important among the cycloalkyl radicals, and of the aralkyl radicals the benzyl, beta phenylethyl, gamma phenylpropyl and phenylpropyl-( 2,2) radicals are especially important.

Suitable aryl radicals are e.g. phenyl, 2-, 3- and 4-methylphenyl, 2-, 3- and 4-ethylphenyl, 4-isopropylphenyl, 4-tert.-butylphenyl, 4 cyclohexyphenyl, 4-bisphenylyl, phenyl-4,5-tetramethylene, 2-, 3- and 4-chlorophenyl, 2,4- dichlorophenyl, 2-, 3- and 4-bromophenyl, 4-fluorophenyl, 4-trifiuorophenyl, 4-acetylphenyl, 4 cyanophenyl, 4-methoxycarbonylphenyl, 4-ethoxycarbonylphenyl, 4-methylsulfonylaminophenyl, 3-methylsulfonylphenyl, 2-, 3- and 4-methoxyphenyl, 2-, 3- and 4-ethoxyphenyl, 4-isopropoxyphenyl, 4-methylmercaptophenyl, and naphthyl-l.

Suitable heterocyclic radicals are e.g. thienyl-2, furyl-Z, pyridyl-2, benzoXazolyl-2 and benzthiazolyl-2.

As anionic radicals X the usual organic and inorganic anions for basic dyes are involved, e.g. there may be mentioned: chloride, bromide, CH SO C H SO p-toluene sulfonate, H SO4 benzene sulfonate, p-chlorobenzene sulfonate, dihydrogen phosphate, phosphate, acetate, chloracetate, formiate, propionate, lactate, crotonate, N0 1 perchlorate, ZnCl and the anions of saturated or unsaturated aliphatic dicarboxylic acids such as malonic acid, maleic acid, citroic acid, oxalic acid, itaconic acid, succinic acid, glutaric acid, adipic acid, pimelic acid and suberic acid. Advantageously colorless anions are preferred for dyeing from aqueous media that do not affect the water solubility of the dye too much. For dyeing from organic solvents such anions are often used that promote the solubility of the dye in organic solvents or at least do not affect the solubility in a negative way.

Dyes of the formula were prepared, in that compounds of Formula III are condensed with heterocyclic aldehydes of Formula IV or functional derivatives thereof in an acid medium that releases an anion X or with addition of a condensation medium that forms an anion X In Formulas II, III and IV A indicates the radicals of a heterocyclic or G-member ring which can be fused to the remaining rings, R is an aryl radical or a heterocyclic aromatic radical, R R R R R and R independently of each other are hydrogen or a non-ionic radical, advantageously alky-l, cycloalky1-, aralkyl, or aryl radicals, whereby R and/or R can be bound to R and/ or R or R, R is hydrogen or a nitrile group, R is alkyl, cycloalkyl, aralkyl or aryl, R can also be bound to a ring fused at A and whereby R R and R can be interconnected with formation of one or more ring system, X stands for an anion and m and n independently of each other signifying the number 0 to 1. The carbocyclic and heterocyclic radicals and the acyclic hydrocarbon radicals contained in these formulas can contain non-ionic substituents.

For carrying out the process that is claimed, suitable compounds of Formula III are for example 3-phenyl pyrazoline A2 3- 4-methylphenyl -pyrazoline- (A2 3- 2-ethylphenyl-pyrazoline- A2 3-(4'-isopropylphenol -pyrazoline- (A2) 3- (4-tertiary butylphenyl) -pyrazoline- (A2) 3- (4'-cyclohexylphenyl -pyrazoline- (A2 3 (4-biphenylyl -pyrazoline- (A2 3- (4'-chlorphenyl) -pyrazoline- (A2) 3- (3 -chlorphenyl) -pyrazoline- A2) 3-(2-chloropenyl)-pyrazo1ine-(A2),

3- (2',4-dichlorphenyl -pyrazoline- A2 3- 3 ,4'-dichlorphenyl -pyrazoline- A2 3- (4'-bromophenyl) -pyrazoline- (A2 3- (4'-fi'uorophenyl -pyrazoline- (A2) 3- 4'-trifluoromethyl -pyrazoline- (A2) 3 4-acetylphenyl) -pyrazoline- (A2) 3 (4'-cyanophenyl) -pyrazo1ine- (A2 3 (4'-methoxycarbonylphenyl) -pyrazoline- A2) 3 (4-ethoxycarb onylphenyl) -pyrazoline- (A2 3- (4'-methylsulfonylphenyl) -pyrazoline- A2) 3 (4-methylsulfonylaminophenyl) -pyrazo1ine- (A2 3- (4-methoxyphenyl) -pyrazo1ine- A2 3 (4'-ethoxyphenyl -pyrazoline- (A2) 3- (4-phenoxyphenyl) -pyrazoline- A2 3- (4-isopropoxyphenyl) -pyrazoline- (A2 3-styryl-5 -phenylpyrazoline- (A2) 3- (p-chlorostyryl -5- 4-chlorophenyl -pyrazoline-(A2) 3- (o,p-dichlorostyryl -5- (2',4'-dichlorophenyl) -pyrazoline- A2 3- (2'-thienyl) -pyrazoline- A2 3- 5-methylthienyl-2' -pyrazoline- (A2) 3- 2'-furyl) -pyrazoline- A2) 3- [5- (o,p-dichlorophenylfuryl-2') ]-pyrazoline- A2 3- 4'-pyridyl -pyrazoline- (A2) 3- (2'-benzoxazoly1) -pyrazoline- A2 3- (2-benzthiazolyl) -pyrazoline- (A2) 3-(1-naphthyl)-pyrazoline-(A2),

3- (2'-naphthyl -pyrazoline- A2) 3-phenyl-4,5-tetramethylenepyrazoline- (A2) 3,4-diphenylpyrazoline- (A2) 3,5 -diphenylpyrazoline- (A2) and the pyrazoline derivative of formula NN-H Suitable compounds of Formula IV are the indolinew-aldehydes tabulated in Table 1, the benz-(c,d) -indole-waldehydes of Table 2, the quinoXalone-w-aldehydes of Table 3, the quinazolone-w-aldehydes of Table 4, 3- methyland (3-ethyl-) Z-methylene-dihydro-(2,3-benzthiazolo-w-aldehyde, 3 ethyl-2-formylmethy1ene-4,S-benzodihydro- (2,3 -benzthiazole, 3,4-dimethyl-Z-formylmethylenedihydro-(2,3)thiazole, 3-rnethyl-2-formylmethylene-dihydro (2,3) benzoxazole, 1,G-dimethyl-2-formylmethy1- ene-dihydro-(1,2)-quinoline and 1-methyl-4-formylmethylene-dihydro-(l,4)-quinoline. Suitable functional derivatives of compounds (IV) are for example acetal, nitrone, azomethine, enamine and salts thereof such as anilinovinyl compounds and the primary products of the Vilsmeier aldehyde synthesis, as well as the corresponding geminal dihalogen compounds.

TABLE 1 Hydro en Methyl H dro on H (1!0 en H Cyano. do y do i Y d E BII T: nggogeni do Methoxy g gtharxy do o 0 en d Phenyl do Y do. 0

do do Methyl Methy ..do

do Hydro en Methyl d do Hydrogen Methyl do do do do do d do do Methoxy do do Ethoxy do d Trifiuoromethyl -do do do Fluoro d do do Chloro do go go dn o o do do Methox do Methylsulphonyl- .do Do. y

amin Do do do Dimethylaminn do D0, D0 "do Methoxycarbonyl- Hydrogen. -do Do. Do --do Hydrogen. Cyano do Do. Do do do Methoxycarbonyl do Do. Acetyl do Do. Phenyl do D0. Hydro en do Phenyi. Cyclohexyl. -do Hydrogen. Hydro en Methoxycarbonvl- Do. do Chloro Do.

TABLE 2 As acid medium anhydrous or aqueous organic and in- R 'l?I-C=(f-CHO organic acids are suitable for the acid medium, e.g. acetic R7 acid, formic acid, propionic acid, chloracetic acid, di- Y chloracetic acid, trichloracetic acid, hydrochloric acid, 5 sulfuric acid and phos horic acid as well as mixtures of P such acids. If an orgamc acid 1s used, it is ossible thou h P g X in general not necessary to add an acid anhydride, e.g.

acetic acid anh dride, for acceleration of the condensa- R7 Ba x 1 tion Hydrogen. Methy Hydr Hydrogen.

Do Ethy on Do. The condensation can also be conducted in inert organic Do 323285;. B8: solvents such as methylene chloride, chloroform, carbon gfgf 3g tetrachloride, ethane tetrachloride, benzene, toluene or yl Do: chlorobenzene with use of a condensation agent such as DO gggigi B8: phosphoroxychloride, phosphortrichloride, phosphorpen- 5 g fgg 3gtachloride or thionyl chloride. GYM": Ethyl7 Do: A preferred embodiment of the present invention con- Hy 13 en- 2: Metggxy g3: sists in the heating of about equivalent amounts (III) and -g" 2, 5 8; (IV) in glacial acetic acid to about C. to the boiling fi O 32 go Brorriiio Hydrcsgen 20 temperature, advantageously to 75-105 C. The separa- O (I 0 rom Do Methy, Hymn Ethyl tion of the dye that is produced occurs 11] the usual way, Do Ethyl Dimethylamino..- Hydrogen. e g by d luting with water and saltlng out with NaCl.

TABLE 3 R0 5 h o o 7 N --CHCHO Methyl Hydrogen. Hydrogem Hydrogen. Hydrogen. Ethyl (in (In (in D0, n-Propy do dn dn D0, iso-propyl do (in do Do, n-Buty'l (In (in (in Do, iso-Buty ,dn (In on 'n-Hexy do do d Do. Benzyl ("In (in (in D B-Phenylethyl dn fin do DO, Oyelohexyl do fin (in Phenyl do rln do Do, Methyl (in do (in Do, D Pheny do o Do. Methy Methy Methyl Y do no Do do Hydrogen. Methyl ..do Do. Do d do Hydrogen. Methyl Do. Dn do do (in Hydrogen- Methyl. D do do Methoxy .do Hydrogen. Dn (in (In Ethoxy .dO-----'.. D0. D0 dn do Chloro do Do.

TABLE 4 V'PreEerrIed dyes of Formula II are those of Formulas 011-0110 an V I OH, N R4 Ra CHa O a N X CH-CHN\ 7 Re I N=O Ra R9 5 7 R10 {t (V) H dro en. H dro on"-.. H dro en. h iiigiigo g y dog y Do R, ir iii i M n l 1 58' 1's R R e y e 4 a n-Butyl--. n .d Do. o Cyclohexyl do Do. Benzyl dn fln Do. X(-) fi-Phenylethy do do D0- \N/ CH=CH-N Methoxyearbonylmethyl Hydrogen "do Do. vr-(lhloropheny Methy do Do. N=O MethyL. do Methy Do.

Do 20 lHllyifi'nven Metlbyg. R (VI) D o e 3 ax ta grass, d th t d 0 I Do Hydrogen. Hydrogen. iso-Propyl. m which R4 an 51 i; 1 e m l g z'l Do Meth Chloro Hydrogen. R 15 an alkyl-, cycloal y ara y or ary ra ic an B8 S8 gfif 33: R stands for a lower alkyl radical, and wherein the D0: Elyd-rgg'em q v D carbocyclic and heterocyclic radicals may contain nonionic substituents.

7 Dyes of the formula R4 /R1 R1 A cc-R1 m-N \CN/ L xv) wherein A, R, R1, R2, R3, R4, R5, R5, R3, X( m and n have the meaning indicated in Formula I, can be prepared if compounds of formula Rs (VIII) in which A, R R R and n have the above indicated meaning, or compounds of formula in which A, R R and n have the above meaning and X is an anionic radical that can be split ofi, or compounds of the formula in which A, R R R and n have the above indicated meaning, X is an anionic radical that can be split off, and X is an anion, or their prior tages with addition of a condensation medium that produces an anion X with pyrazolines of the formula in which R, R R R R and m have the above indicated meaning, are reacted and-in case R stands for hydrogenpossibly an alkyl, cycloalkyl, or aralkyl radical is introduced subsequently. In the reaction of compounds of Formula IX with Formula XI and the possible introduction of alkyl, cycolalkyl, or aralkyl radicals, dyes are produced corresponding to Formula I wherein R is hydrogen, an alkyl, cycloalky, or aralkyl radical.

Compounds of Formula VHI which are suitable for the reaction of the invention are for example N-isoamyl naphtholactarn-( 1,8),

N-n-hexyl naphtholactam-( 1,8

N-cyclohexyl naphtholactam-( 1,8 N-benzyl-naphtholactam-( 1, 8 N-beta-phenylethyl naphtho1actam-( 1, 8 N-gamma-phenyl-n-propylnaphtholactam-( 1, 8) N-phenyl naphtholactarn-( 1,8 N-methoxycarbonylmethyl-naphtholactam-( 1,8 N-beta-cyanethyl naphtholactam-( 1,8 N-beta-chlorcthylnaphtholactam-( 1,8 N-beta-ethoxycarbonylethyl naphtholactam-( 1,8 N-w-methoxyethyl naphtholactam-( 1, 8), N-beta-dimethylamino ethyl naphtholactam-( 1,8), N-b eta-morpholinoethyl naphtholactam-( 1, 8), N-methyl-4-chlor-naphtholactam-( 1,8 -N-ethyl-4-bromonaphtholactam-( 1,8 N-ethyl-4-hydroxynaphtholactam- 1,8 N-ethyl-4-methoxy naphtholactam-( 1,8 N-ethyl-4-n-butoxynaphtho1actam-( 1,8 N-ethyl-4-dimethylamino naphtholactam- 1, 8), N-ethyl-4-nitronaphtho1actarn- 1,8) N-ethyl-4-acetyl naphtholactam-( 1,8 N-ethyl-4-methyl-naphtholactam-( 1, 8), N-methyl-S-chloro naphtholactam- 1,8 N-methy1-2-ethyl-naphtholactam-( 1, 8) N-ethyl-2,4-dichlor naphtholactam-( 1,8 N-ethyl-2,4-dibrom naphtholactam- 1,8 N-n-butyl-4-brom-naphtholactam-( 1, 8) N-methyl-7-methoxy-naphtholactam-( 1,8) N-ethyl-4-beta-methoxy ethoxynaphtholactam-( 1,8 N,2-trimethylene naphtholactam-( 1,8 N,2-trimethylene 4-ch1oronaphtholactam-( 1,8 N,2-trimethylene-4-brom naphtholactam-( 1,8

acridone, N-methyl-acridone, N-ethylacridone, N-n-propyl acridone, N-iso-propyl acridone, N-n-butylacridone, N- iso-butyl acridone, N-n-amyl acridone, N-isoamyl acridone, N-n-hexyl acridone, N-neopentyl acridone, N-phenylacridone, N-benzyl acridone, N-beta-phenylethylacridone, N-cyclohexyl acridone, N-allyl acridone, l-chloro acridone, 2-chloroacridone, 2-chloroacridone, 4-chloroacridone, l-bromacridone, 2-bromacridone, 3-bromacridone, 4-bromacridone, as well as their N-methyl and N- ethyl derivatives, l-methoxy acridone, 2-methoxy acridone, 3-methoxy acridone, 4-methoxy acridone, l-ethoxy acridone, 2-ethoxy acridone, 3-ethoxy acridone, 4-ethoxy acridone, Z-n-butoxy acridone, 2-phenoxy acridone, 2- methylmercapto acridone, Z-methylsulfonyl acridone, 2- dimethylamino acridone, Z-diethylamino acridone, 2- methylacridone, 4-methyl acridone, Z-ethyl acridone, 4- ethyl acridone, 4-isopropy1 acridone, 3-hydroxy acridone, 1,4-dimethoxy acridone, 2,4-dimethoxy acridone, 2,7-dimethoxy acridone, 2,7-diethoxy acridone, 2-methoxy-7- chloroacridone, N,4-trimethylene acridone, N-beta-cyanethyl acridone, N-beta-chlorethyl acridone, N-beta-methoxyethyl acridone, N-beta-ethoxyethyl acridone, N-betaethoxycarbonyl acridone, N-methoxycarbonylmethyl acridone and N-beta dirnethylaminoethyl acridone, anthrapyridone (Formula XII), N-methyl anthrapyridone, N-nbutyl anthrapyridone, N-beta-ethoxyethyl anthrapyridone, Z-methyl anthrapyridone, 6-methyl anthrapyridone, 4-dinethylamino anthrapyridone and 4-anilino anthrapyrione.

(XIII) (XIV) (XV) anthrapyrimidone (Formula XIH), N-methyland N-ethyl anthrapyrimidone.

Suitable compounds of Formula IX are for example 2- methylmercaptobenz (c,d) indole, 2 ch1or-benz-(c,d)- indole, 9-chlor-acridine, 9-fluor-acridine, py-chlor anthrapyridine (Formula XIV) and py-chlor anthrapyrimidine (Formula XV) as well as 9-chloroacridine which is produced in the treatment of the diphenylamine-Z-carboxylic acids of Table in which R is hydrogen, with phosphoroxychloride and/or phosphorpentachloride.

Suitable compounds of Formula X are for example the hydrochloric acid, sulfuric acid or acetic acid salts of the above mentioned compounds (IX) or their quaternary salts obtained with e.g. dimethylsulfate, diethylsulfate, toluene sulfonic acid methyl ester or benzyl chloride.

According to the invention suitable preliminary stages for the preparation of the compounds of Formulas VIII, IX, and X are diphenylamino-Z-carboxylic acids of the formula I la (XVI) in which R is hydrogen, an alkyl-, cycloalkyl-, aralkylor aryl radical, and the benzene nucleus may present substituents.

The designation preliminary stage does not mean however that the diphenylamine carboxylic acids are in any case first cyclized to acridine derivatives and only subsequently condensed with pyrazolines: the reaction steps can rather be transposed, i.e. first a compound of the formula is (XVII) wherein R, R R R R R and m have the indicated meaning, is prepared, which by cyclizing with (formal) water slitting 01f (presumably in the course of at least one further intermediate stage) the dye is prepared.

Suitable compounds of Formula XVI are for example the diphenyl amino-2-carboxylic acids of the following table:

TABLE 5-+Cont1nued Rs Substltuent fi-Methoxyethyl. 4,5'-dimethoxy. B-Dimethylaminoet Hydrogen- Do. 6-methyl.

Do 4-iso-propyl.

Do. 4-hydroxy.

Do- 4-methoxy.

Do 4-iso-propoxy.

D 4-ethoxy.

Do. 4,4-diethoxy.

Do 3,5-diethoxy.

D0 4,6'-diethoxy.

Substituents or fused rings Hydrogen 4-ehloro-4,6-dieth0xy.

Do 4-dimethylamino.

D0. 4-d.iethylamino.

D0 4-ehloro-4-diethylamino.

Do 3,4-benzo.

Do 3,4-benzo-4'-ethoxy.

Do 4-methoxycarbonyl.

Do 3-ethoxycarbonyl.

Do 4-methylsulfonylamino.

Do 4-dimethylanndocarbonylamino.

Do 4-methoxycarbonylamino.

D0 4-rnethylsulfonyl.

Do 3-methyl-4-methoxy.

Do 5-methoxy-4-methyl.

Do 6-methoxy-4-ethoxy.

Do 4,5-dieh1oro-4-eth0xy.

Further suitable compounds of Formula XVI are for example the compounds which present the following structure:

00 011 0 (Int,

H 00 on N o=o 3 H:

I =0 N -N OCHz GOOH i Q-rQ-i cm on:

H N-C= 000E N N H H Y a N--C=O o o o 11 I COOH 1 1 and C O O H @-H@ Hz H2 Suitable pyrazolines of Formula XI are described as those of Formula HI in col. 2.

Of the dyes of the general Formula VII those of Forwherein R and X have the meaning indicated above, R stands for an aryl radical or a thienyl radical and the rings and acyclic radicals may present the non-ionic substituents that are conventional in the chemistry of cationic dyes.

Dyes of Formula XIX can be prepared in that compounds of the formulas or (c) (XXI) in which R has the meaning indicated above and can be joined with the naphthalene ring, X stands for a radical that can be split 01f anionically, especially a mercapto group or a halogen atom, X is an anion, and wherein R and the naphthalene ring may contain non-ionic substituents that are conventional in the chemistry of cationic dyes, are condensed with pyrazolines of the general formula CHg-CH in which R, has the meaning indicated above, and in case R stands for hydrogen an alkyl, cycloalkyl or aralkyl radical is introduced subsequently.

Dyes of Formula XX can be prepared when compounds of formulas X1 X1 O l) O K) y 15., it.

(a) or (b) or (c) (XXIII) or their preliminary stages of Formula XVI wherein R has the meaning indicated above, X stands for a radical that can be split off anionically, X is an anion, and wherein the acridine or acridone ring may contain nonionic substituents that are customary in the chemistry of cationic dyes, are condensed with pyrazolines of the general formula Gui-on,

Nzo

wherein R has the meaning indicated above, and in case R stands for hydrogen an alkyl, cycloalkyl or aralkyl radical is introduced subsequently.

If a starting product of Formula a is used for preparation of the dyes of Formula XIX or XX, it is necessary to effect the condensation with addition of a condensation agent that releases an anion X For carrying out the process of the invention a compound of Formula VIII or XVI for example is heated with an equivalent amount of a pyrazoline of Formula XI in an inert diluent with addition of a condensation agent that releases an anion X One of the components may also be used in excess. As diluent there are advantageously those which comprise fluids that are inert with reference to the condensation medium whichpossibly under vacuumcan be readily removed by distillation, e.g. methylene chloride, chloroform, carbon tetrachloride, ethane tetrachloride, ethylene trichloride, dichlorethane, chlorobenzene, dichlorobenzene, benzene, or toluene. As condensation medium acid chlorides such as phosphoroxychloride, phosphoroxybromide, phosphor-, triand pentachloride, thionylchloride and phosgene can be used. These condensation media can often be used also in such excess that they act also as solvents or diluents. This is especially true of phosphoroxychloride. The rate of condensation can be increased by supplementary use of other Water-splitting agents such as aluminurnchloride, titanium tetrachloride or phosphorpentoxide.

In a modification of the process, a compound for Formula IX or X is condensed with a pyrazoline of Formula XI or )OCII. For these processes it is generally not necessary to add a condensation agent. Rather it is sufficient to heat compound IX or X in a suitable solvent with the pyrazoline. The optimal temperature depends upon the structure of the components and can very readily be determined empirically because the beginning of condensation is associated with a color efiect: in general, heating up to about C. will lead to the desired result. As solvent there may be used for example alcohols such as methanol, ethanol, nand isopropanol, iso-amylalcohol, glycol, glycolmonomethylether and glycerol, ethers such as diethyleneglycol-dimethyland diethylether and dioxan, also pyridine, quinoline, dimethyl formamide, N-methylpyrrolidone, tetrachlorethane, chlorobenzene and o-dichlorobenzene. The water-soluble solvents with high boiling point are preferred because they allow an especially simple way of operating.

The type of anion X is generally not important for the coloring properties, and it is given by the method of preparation and the possible purification of the crude dye. In general the dyes are present as halides (particularly as chlorides or bromides) or as methosulfates, ethosulfates, sulfates, benzenes or toluene sulfonates or as acetates. The anions can be exchanged in any way for other anions e.g. tetrafiuorborate, phosphate, chlorozincate, nitrate, perchlorate, oxalate, propionate, formiate, citrate, tartrate, lactate or benzoiate ions.

In order to achieve solubility in media suited for dyeing from organic solvents, these anions can be exchanged for e.g. Z-ethylcaproic acid, lauric acid, oleic acid, linoleic acid, a mixture of aliphatic carboxylic acids with 15 to 19 carbon atoms (Versatic Acid 1519, Shell Company), a mixture of aliphatic carboxylic acids with 9 to 11 carbon atoms (Versatic Acid 911, Shell Company), cocoa fat acid first running, tetradecanoic acid, undecylenic acid, dimethyl propane acid, dimethyl acetic acid, carboxylic acids whose carbon chain is broken by heteroatoms, e.g. nonylphenoltetraethylene glycolether propionic acid, nonylphenol diethylene glycolether propionic acid, dodecyltetraethylene glycolether propionic acid, 3-(nonyloxy)- propionic acid, 3-(isotridecyloxy)-propionic acid, 3-(isotridecyloxy)-diethylene glycolether propionic acid, ether propionic acid of the alcohol mixture with 6 to 10 carbon atoms, nonylphenoxyacetic acid, aromatic carboxylic acids such as tert.-butyl benzoic acid, cycloaliphatic carboxylic acids such as hexahydrobenzoic acid, cyclohexene carboxylic acid, abietic acid and sulfonic acids such as tetrapropylene benzene sulfonic acid and dedecylbenzene sulfonic acid.

The new products are valuable dyes which can be used for the dyeing and printing of natural and synthetic materials, e.g. leather, mordanted cotton, cellulose, synthetic superpolyarnides and superpolyurethanes as well as for the dyeing of lignin-containing fibers such as coco, jute and sisal. They are also suitable for the preparation of writing fluids, stamping dyes, ball pen pastes, and they can be utilized also in rubber printing.

They are particularly suitable for the dyeing from aqueous baths or from organic solvents and printing of filaments, strips, fabrics and knit goods of polyacrylonitrile or copolymers of acrylonitrile and other vinyl compounds such as vinyl chloride, vinylidene chloride, vinyl fluoride, vinyl acetate, vinyl pyridine, vinyl imidazole, vinyl alcohol, acrylic and methacrylic acid esters and amides, asymmetric dicyanoethylene, or linters, fibers, yarns, webs, fabrics and knit goods of acid modified aromatic polyesters as well as acid modified polyamid fibers. Acid modified aromatic polyesters are for example polycondensation products of sulfoterephthalic acid and ethylene glycol, i.e., sulfonic acid group containing polyethyleneglycol terephthalates (type, Dacron 64 of E. I. du Pont de Nemours and Company) as described in Belgian Pat. No. 549,179 and US. Pat. No. 2,893,816.

The dyeing can be effected from weakly acid baths whereby the material is advantageously introduced into the bath at 40 to 60 C. and then dyed at boiling temperature. Under pressure it is also possible to dye at temperatures above 100 C. Moreover, the dyes can be added to spinning solutions for the production of polyacrylonitrile containing yarns, or they can be applied to unstretched filaments.

The dyeing and printing-especially on the last named materialsis characterized by outstanding resistance, primarily to light, moisture, decatizing, sublimation, sweat, crocking, and in many cases it is characterized by the clarity of the color tone. The new dyes present desired reserve effects, i.e. selective dyeing so that such fibers as intermixed wool or polyester are not dyed.

For application of the dyes to the materials the known processes of dyeing and printing including dyeing from organic solvents (e.g. chlorated hydrocarbons) can be utilized.

The parts indicated in the examples are parts by weight.

EXAMPLE 1 and is suitable for the dyeing, printing and bulk dyeing of polyacrylonitrile or acid modified polyesters in extraordinarily brilliant and very fast greenish yellow tones. The yield is almost quantitative.

If instead of the above mentioned aldehyde, equivalent amounts of one of the following aldehydes is used, very valuable yellow dyes of analogous structure are obtained with operating conditions otherwise unchanged: S-methoxy-, S-ethoxy, 5-benzyloxy-, 5-phenoxy-, S-methyl, 5- ethyl, 5-benzyl-, 5-phenyl-, 5-chloro-, 5-flu0ro-, S-trifluoromethyl-, 5-methylsulfonyl-, 7-methyl, 7-ethyl-, 7-methoxy-, 7-chloro-5,7-dichloro-, 5,7-dimethoxy-, 4,6-dimethyl-, 4,6-dichloroand 4,7-dimethoxy-1,3,3-trimethyl-2- methylene-indoline-w-aldehyde, 1-ethyl-3,3-dirnethyl-, 1- benzyl-3,3-dimethyland 1-phenyl-3,3-dimethyl-2-methylene-indoline-w-aldehyde. These aldehydes are prepared in the same way as the above mentioned aldehyde by Vilsmeir formylation of the corresponding Z-methyleneindoline.

EXAMPLE 2 parts 1,3,3-trimethyl-2-methylene-indoline-w-aldehyde and 88 parts 3-(4'-methoxyphenyl)-pyrazoline-(A2) are heated to about 100 C. for 90 minutes with 500 parts glacial acetic acid. Workup as in Example 1. The yellow dye of formula CH3 CHa cm-on, H CH 01 -o N is obtained with very good yield. This dye has outstanding properties for the dyeing, printing and bulk dyeing of polyacrylonitrile and acid modified polyesters.

The 3 (4-methoxyphenyl)-pyrazoline-(A2) was prepared by heating the Mannich base obtained from 4-methoxyacetophenone, paraformaldehyde and dimethylamine with an excess of hydrazine hydrate in methanol with addition of soda lye and purified by fractional distillation under vacuum (boiling point =160 C.). The structure was verified by analysis and mass spectroscopy. The following pyrazolines were similarly prepared which-if the process of Example 2 is applied with use of equivalent amounts of one of these pyrazolines-also yield very pure yellow dyes of corresponding structure:

3-(4'-ethoxyphenyl pyrazoline (A2) 3- 4-methylphenyl) -pyrazoline- A2) 3 (4'-ethylphenyl) -pyrazoline- A2 3- (4'-biphenylyl) -pyrazoline- (A2) 3- (3 '-rnethoxyphenyl) -pyrazo1ine- A2 3-( 3,5'-dimethyl-phenyl) -pyrazoline-(A2) 3- (4-chlorphenyl) -pyrazoline- (A2 3- (3 ',4'-dichlorphenyl) -pyrazoline- (A2 3- (4'-bromphenyl) -pyrazoline- A2 3 4-cyanphenyl -pyrazoline- A2 3- (4'-fluorphenyl) -pyrazoline- (A2) 3-( 4'-trifluormethylphenyl -pyrazoline- A2 3- 4'-methylsulfonylphenyl) -pyrazoline- A2 3- (4'-methy1 sulfonylaminophenyl) -p yrazoline- (A2 3 -styryl-5-phenylpyrazoline- A2 3 (4'c-lchlorstyryl) -5- 4'-chlorphenyl) -pyrazoline- A2) 3 -thienyl- (2'-) -pyrazoline- (A2) EXAMPLE 3 25.9 parts 1,3,3 trimethyl-S-methoxycarbonyl-Z-methylene indoline-w-aldehyde and 14.6 parts 3-phenylpyrazoline-(A2) were heated in to 200 parts chloroform with 15 to 20 parts phosphortrichloride or phosphoroxychloride for 30 to 40 minutes to boiling. After distilling off of the chloroform and recrystallization of the residue from water with addition of activated charcoal the dye of formula was obtained, which yields a very fast and clear yellow color or print on polyacrylonitrile and acid modified polyester.

EXAMPLE 4 19.1 parts 3-methyl-2-methylene-dihydro(2,3)-benzthiazole-w-aldehyde and 14.6 parts 3-phenylpyrazoline-(A2) were heated in about 100 parts glacial acetic acid for 1 to 2 hours at about 90 C. After cooling to a temperature below 50 C. the dye solution was poured into 500 to 1000 parts water. After addition of about 50 parts NaCl the dye of formula was sucked off. The yield in chromatographically pure dye was practically quantitative. The dye produces a yellow dye and print on the materials indicated.

If instead of 3-phenyl pyrazoline an equivalent amount of one of the pyrazolines listed in Example 2 is used, there is also a valuable yellow dye as product of an otherwise unchanged process.

EXAMPLE 5 17.5 parts 3-methyl2-formylmethylene-dihydro (2,3)- benzoxazol (prepared according to Brooker, US. Pat. 2,165,692, Example are condensed by the process of Example 4 with 14.6 parts 3-phenyl-pyrazoline-(A2). The dye of the formula is obtained, which yields extraordinarily clear green-tinged yellow dyes and prints on polyacrylonitrile, acid modified polyester and acid modified polyamide.

If instead of 3-phenyl pyrazoline an equivalent amount of one of the pyrazolines listed in Example 2 is used, a valuable green-tinged yellow dye is obtained as product of an otherwise unchanged process.

EXAMPLE 6 7.6 parts 3-(2'-thienyl)-pyrazoline-(A2) and 11.0 parts of the aldehyde of formula (prepared according to the indications of Example 1 of Belgian Pat. 647,036) are heated with 50 parts glacial acetic acid for 1 hour at about 90 C. Upon dilution of the cooledmixture with about 750 parts water there is obtained a deep red solution from which when about 50 parts saturated salt solution is added the dye of formula changed process.

EXA MPLE 7 24.4 parts of the aldehyde of formula \N/-CH--CHO and 15.2 parts 3-(2-thienyl)-pyrazoline-(A2) are heated with to parts glacial acetic acid for 1 to 2 hours at about 90 C. The mixture, cooled to about 50 C., is diluted with 1 to 2 liters water. After addition of NaCl solution the dye of formula is separated out with very good yield. The dye when applied to the specified materials produces very fast brilliant orange dyes and prints.

The aldehyde that was used was prepared in the following manner: o-chlornitrobenzene was heated with an excess of n-propylamine with addition of copper powder in an autoclave for 5 hours at -180 C. (9-10 atm.). The nitropropylaniline was freed from the reaction product with soda lye. By vacuum distillation it was purified (boiling point -'135 C.) and then converted to 2- amino-N-n-propylaniline by reduction with stannic-(II)- chloride in glacial acetic acid or by catalytic hydration (Raney nickel). The product was reacted in aqueous HCl solution at 6070 C. With acetylcarboxylic acid. In this process an oil first separated out which solidified upon neutralizing of the cooled mixture with soda lye. The product thus obtained was purified by distillation (boiling point =145147 C.). An oil was obtained which crystallized upon being rubbed with cyclohexan. The melting point is 51 C. Values on analysis correspond to the formula (B-CHa This compound was methylated by dropping from a heatable drop funnel into excess dimcthylsulfate at 80-90" C.

From the salt thus obtained, by treatment with aqueous soda solution, the methylene base of the formula 18.5 parts l-methyl-4-formylmethylene-dihydro-(1,4)- quinoline (prepared as in Brooker, US. Pat. 2,165,692, Example 9) and 14.6 parts 3-phenyl-pyrazoline were heated with 100 parts glacial acetic acid for 45 minutes at about 90 C. From the cooled mixture, there is obtained by thinning with water and addition of NaCl the dye of formula which yields orange dyes and prints on the specified materials.

If instead of 3-phenylpyrazoline an equivalent amount of one of the pyrazolines listed in Example 2 is used, a valuable orange dye is also obtained with no other change in the procedure.

EXAMPLE 9 19.7 parts N-ethyl-naphtholactam-(1,8) and 14.6 parts 3-phenyl pyrazoline-(AZ) were dissolved in 60 parts chloroform. 20 parts phosphoroxychloride were allowed to run in, whereby the temperature rose to the boiling point of the solvent, and the mixture was kept boiling for another hour. The crude dye remaining after distilling off of the chloroform was dissolved in 700 parts boiling water and treated with activated charcoal. From the filtrate there separated upon cooling of the main mass the dye of formula in crystalline form. The remainder was precipitated by addition of NaCl. The dye is suitable for the dyeing, printing and bulk dyeing of materials which consist entirely or preponderantly of polyacrylonitrile, in extraordinarily fast, very clear fluorescent yellow hues.

If instead of 3-phenyl-A2-pyrazoline, equivalent amounts are used of 3-4'-methylphenyl-, 3-4'-ethylphenyl-, 3-3- methylphenyl-, 3-4-methoxyphenyl, 3-4-ethoxyphenyl-, 3-3',4'-dimethoxyphenyl, 3-4 chlorphenyl, 3-4-bromphenyl-, 3-4'-cyanphenylor 3-alpha-thienyl-AZ-pyrazoline, with no other change in the process there are also obtained very pure yellow dyes.

18 EXAMPLE 10 169 parts naphtholactam-(1,8) and 146 parts 3-phenylpyrazoline-(AZ) were stirred in 750 parts chlorobenzene with 150 parts phosphoroxychloride for 2 /2 hours at C. Thereafter the residual condensation agent was decomposed by dropping in of water and the solvent was steam distilled off. There was thus obtained an aqueous dye solution. Upon cooling the dye of formula CH3-CH1 H separated out in crystalline form. This dye was suitable for the dyeing of polyacrylonitrile, in very fast yellow tones.

The dye can be converted in the usual way, e.g. by stirring with dilute aqueous soda solution at about 50 C. into the dye base of formula CHI-CHI N: C N

This compound melts after crystalization from methylcyclohexan or toluene at 186-188 C.

EXAMPLE 11 29.7 parts of the dye base of formula in up prepared as in Example 10 are dissolved in 50-100 parts dry dimethylformamide. At about 100 C. 13.0 parts acid free dimethylsulfate is allowed to run in, with stirring, and stirring is continued for another 1 to 3 hours at about 100 C. and the dye solution cooled to about 50 C. is diluted with 900 parts water. By addition of NaCl the dye of formula CHi-CHQ CHE-N:

is separated out.

If instead of dimethylsulfate, equivalent amounts of diethylsulfate, ethylenechlorhydrin, beta-dimethylaminoethyl chloride, beta-diethylaminoethyl chloride, beta piperidinylethyl chloride, beta-morpholinoethyl chloride, betaethoxyethyl chloride, beta-chloroor beta-brom-propionitrile or l-iodobutane is used, a fast yellow dye is also obtained.

EXAMPLE 12 27.6 parts N-ethyl-4-brom-1,8-naphtholactam and 14.6 parts 3-phenyl-A2-pyrazoline are stirred with 100 parts freshly distilled phosphoroxychloride for 2 to 4 hours at 70 to 80 C. Thereafter the main amount of the phosphoroxychloride is distilled off under vacuum at a temerature below 80 C. The residue is first decomposed densation agent. After completion of the hydrolysis the 1 9 with 750 parts water and then boiled out. From the filtrate there separates the dye of formula:

which dyes polyacrylonitrile with very good properties of resistance in very clear pronouncedly red-tinged yellow hues.

If instead of the above indicated naphtholactam derivative one of the following compounds is used in equivalent amount, pure coloristically similar dyes are obtained: N-methyl4-brom-, N-n-propyl-4-brom-, N-isopropyl-4- brom-, N-n-butyl-4-brom-, N-isoamyl-4-brom-, N-n-hexyl- 4-brom-, N-methyl-4-chloro-, N-ethyl-2,4-dichloro-, N- methyl-5-chloro-, N-methyl-2,4,5-trichloro-, N-methyl-S- brom-, N-ethyl-4-acetyl-, N-ethyl-4-acetylamino-, N-ethyl- 4-methyl sulfonylamino-, N-ethyl-4-dimethylamino-, N-

32.5 parts of the salt of formula CHaN=C- 3 CH5 l C: CHaS O and 17.6 parts 3-4-methoxyphenyl-AZ-pyrazoline are heated in 100 parts dimethyl formamide until the completion of the splitting off of methylmercaptan at 100 to 110 C. After dilution with water the dye of formula ethyl-4-methoxy-, N-methyl-6-methoxyand N-methyl-6- 5 /CH1CH, (H methylaminonaphtholactam-( 1,8 CH;N=CN\ EXAMPLE 13 209 parts N,2-trimethylene naphtholactam-(1,8) and 146 parts 3-phenyl-A2-pyrazoline were stirred with 750 parts freshly distilled phosphoroxychloride with addition of 70 to 150 parts phosphorpentoxide for 4 to 6 hours at about 60 C. Thereafter the cooled mixture was poured into 5000 parts water for decomposition of the excess conseparated dye of formula CHr-CH;

I Q onisom is separated in the usual way. It yields brilliant, very pure yellow dyeings and prints on polyacrylonitrile with good fastness properties.

EXAMPLE 16 22.5 parts N-n-butylnaphtholactam-(1,8) and 22.2 parts I I N L 3,S-diphenyl-AZ-pyrazoline are condensed together as in c1 the indications of Example 9. The dye of formula was purified by crystallization from water with addition J: of charcoal. The dye yields very fast bright green-tinged H a 01H yellow dyes and prints on materials made of polyacrylo- CH3 CH2CH2CH2 N=C N nitrile.

If instead of the N,2-trimethylenenaphtholactam, equiv- N=C alent amounts of 2-methyl-, 2-ethyl-, 2-isopropylor N- methyl-Z-ethyl-naphtholactam (1,8) is used, with otherwise unchanged procedure very fast green-tinged yellow dyes are also obtained.

EXAMPLE 14 222 parts N-beta-cyanethyl-1,8-naphtholactam and 152 parts 3-alpha-thienyl-A2-pyrazoline are condensed in 750 parts chloroform with to 200 parts phosphoroxychlois obtained which is suited for the dyeing, bulk dyeing and printing of polyacrylonitrile, in very pure yellow tones. If instead of 3,S-diphenyl-AZ-pyrazoline equivalent amounts of one of the following AZ-pyrazolines is used, conforming to the general Formula XI, a very fast yellow dye is also obtained;

R3 R4 R2 R! R m Phenyl Hydr Hydro e Hydro en Phenyl 1 Hydrogen d0 Phenyl- -.do do 0 Math Methyl Hyd do 0 Cyclohexyl do -.do do 0 R1+R2= Cyclohexyl -do..- 0 D Cyclohexy1- Hydrogen. ..do 0 Dn Hydro en Methyl M do.. 0 Do -do Hydrogen Hydrogen p-Methoxyphenyl- 0 Do .do d0 do Alpha thienyl 0 ride according to the method indicated in Example 9. EXAMPLE 17 The dye of formula CHr-CHg at an 1 7 steam. The dyestufi of Example 10 is thus obtained.

21 EXAMPLE 18 193 parts N-methylacridone and 146 parts 3-phenyl-A2- pyrazoline are heated in 1000 parts o-dichlorobenzene with 250 parts phosphoroxychloride for 5 hours at about 120 C. Thereafter the mixture is allowed to cool, the excess phosphoroxychloride is decomposed by cautious addition of water and the o-dichlorobenzene is driven off with steam. From the aqueous solution thus obtained, the dye partly separates upon cooling. The separation is completed by addition of NaCl. The dye thus obtained, of

formula CHr-N can be purified by crystallizing from water with addition of charcoal. The dye is suitable for dyeing, printing and bulk dyeing of materials that wholly or preponderantly comprise polyacrylonitrile or acid modified polyesters or acid modified polyamides, in outstandingly fast yellow hues.

If instead of 3-phenyl pyrazoline the equivalent amount of one of the pyrazolines listed in Example 9, last paragraph, very fast yellow dyes are also obtained.

EXAMPLE 19 CHz-CHz 239 parts 2-ethoxy-acridone and 146 parts 3-phenyl-A2- pyrazoline are condensed according to the indications of Example 18. A strong red-tinged yellow dye is obtained, of formula which yields very fast dyes and prints on the specified materials.

If instead of 2-ethoxy-acridone the equivalent amount of the acridones listed in the following table are used, corresponding dyes are obtained which y ield very fast dyes and prints on polyacrylonitrile materials as indicated in the table.

22 TABLE-Contlnuerl Acridone: Color on polyacrylonitrile 2-bromacridone Red-tinged yellow. 2,7-dichloroacridone Do. 2,7-dibromacridone Do. Z-methylacridone Do. 2-ethylacridone Do. 4-isopropylacridone Yellow. 3-phenylacridone Red-tinged yellow. Z-cyclohexylacridone Do. Z-dimethylaminoacridone Violet. 2-diethylaminoacridone Do.

EXAMPLE 20 213 parts diphenylamine-2-carboxylic acid is heated with 500 parts phosphoroxychloride for 1 /2 hours at about C. Then at about 50 C. there is added portionwise 146 parts 3-phenylpyrazoline-(A2), and the mixture is stirred for another 2% hours at about 50 C. and then with rapid agitation and thorough cooling it is allowed to run into 1000 parts water. A yellow suspension is obtained. After complete hydrolysis of the phosphoroxychloride the product is sucked OE and washed with cold water. In very good yield, there is obtained the dye of which can be purified by crystallization from water, but in general this is not necessary. The product is suitable for the dyeing of polyacrylonitrile in fast yellow hues. The dye can be converted by stirring with dilute soda solution into the dye base of formula This compound can be crystallized from methylcyclohexan, for example, and it melts then at 158 C. By quaternizing this dye base with dimethylsulfate in toluene at 70 to 100 C. there is obtained the dye of Example 18 in the form of methosulfate. Fast yellow dyes are also obtained with diethylsulfate or another quaternizing agent listed in Example 11.

EXAMPLE 21 213.5 parts 9-chloroacridine and 176 parts 3-(4'-methoxyphenyl)-pyrazoline-(A2) are slowly heated to to C. with 750 parts chlorobenzene and held at this temperature for 2 to 3 hours. Thereafter the solvent is steam distilled off. The residue is stirred with excess lime solution or soda lye whereby the dye base of formula 0 CH: N:C N

CHg-CH] is liberated. This compound can be purified by crystallization from toluene. Orange red crystals are obtained, which melt at 210 to 214 C.

The salts of this compound with inorganic and organic acids such as hydrochloric acid, hydrobromic acid, sulfuric acid, methyl sulfuric acid, phosphoric acid, amidosulfonic acid, methansulfonic acid, benzene and paratoluene sulfonic acid, formic acid, acetic acid, lactic, acid, chloro-, diand trichloroacetic acid, propionic acid, butyric and isobutyric acid as well as the quaternary salts, e.g. with the quaternizing agents of Example l1 are suitable for the dyeing, printing and bulk dyeing of the materials specified in various examples, in very fast red-tinged yellow hues.

EXAMPLE 22 257 parts 4'-ethoxyphenylamine-2-carboxylic acid and 400 to 500 parts phosphoroxychloride are heated to 90 C. for 2 /2 hours. Thereafter at 40 to 50 C. there is added 152 parts 3-(alpha-thienyl)-pyrazoline-(A2) and the mixture is stirred for another 2 hours at about 50 C. and the porduct is worked up as indicated in Example is obtained, which yields outstandingly fast orange-red color and prints on the materials mentioned in the previous examples.

If instead of 4-ethoxydiphenylamine-Z-carboxylic acid there is used an equivalent amount of 4-methoxy-, 4'-npropoxy-, 4-isobutoxy-, 4-phenoxy-, 3',4'-dimethoxy-, 2',4'-dimethoxy-, 2',5'-dimethoxy-, 2',5'-diethoxy-, 3',5'-diethoxy-, 4,4'-diethoxy-, 4-chloro-4-ethoxy-, 4,4-dichloro- 4-methyl-, 4'-ethyl-, 4'-phenyl-, 4'-cylohexylor 4'benzyldiphenylamine-2-carboxylic acid, fast orange red dyes are also obtained. If instead of thienyl pyrazoline the equivalent amount of 3-4'-methoxyphenyl-, 3-4'-ethoxyphenyl-, 3-4-n-butoxyphenylor 3-4-isoamyloxyphenyl- A2-pyrazoline is used, very fast dyes with an orange red tone are obtained. These dyes can be converted in the usual way into the basic color bases which can be quaternized with suitable alkylating agents. The quaternary salts thus obtained with the agents listed in Example 11 yield outstandingly fast dyes and prints on polyacrylonitrile.

EXAMPLE 23 A mixture of 13.0 parts N-methyl anthrapyridone, 7.3 parts 3-phenyl pyrazoline-(A2), 75 parts o-dichlorobenzene and 10 parts phosphoroxychloride is heated at about 120 C. for 5 hours. On cooling, the dye of formula I CHa-CH: CH3

separates out in crystalline form. For purification it is sufiicient to wash the crude product with a suitable solvent, e.g. benzene or ethylene chloride, but the dye can also be purified by crystallization from water. It dyes polyacrylonitrile with a good lightfast orange.

If instead of phenylpyrazoline an equivalent amount of 3-(alpha-thienyl)-pyrazoline- (A2), 3-(4'-methoxyphenyl)- pyrazoline-(A2), 3(4'-ethoxyphenyl)-pyrazoline-(A2) or 3- (4'-diethylaminoethoxyphenyl)-pyrazoline- (A2) is used, with the same procedure, dyes are obtained which dye polyacrylon trile with a very good lightfast orange.

EXAMPLE 24 A fabric of polyacrylonitrile is printed with a printing paste which is prepared in the following way: 30 parts by weight of the dye of formula CHz-CH:

Acid modified polyglycolterephthalate fibers are placed in an aqueous bath at 20 C. with a bath ratio of 1:40, the bath containing per liter 3 to 10 g. sodium sulfate, 0.1 to 1 g. oleylpolyglycolether (50 moles ethylene oxide), 0 to 15 g. dimethylbenzyldodecylammonium chloride and 0.15 g. of the dye of formula and adjusted to a pH of 4 to 5 with acetic acid. The mixture is heated in less than 30 minutes to C. and the bath is held at this temperature for 1 hour. Finally the fibers are rinsed and dried. A yellow dye with very good properties of resistance is obtained.

EXAMPLE 26 Polyacrylonitrile fibers are placed in an aqueous bath at 40 C. with a bath ratio of 1:40, the bath containing per liter 0.75 g. 30% acetic acid, 0.38 g. sodium acetate and 0.15 g. of the dye of formula .21. as u The bath is heated to boiling within 20 to 30 minutes and the bath is held at this temperature for 30 to 60 minutes. After rinsing and drying there is obtained a yellow dye with very good properties of resistance.

EXAMPLE 27 In a dye vessel of 500 ml. capacity which is in a heated water bath, 0.055 g. of the dye of formula CH:- C H:

is pre-mixed with 20 times the quantity of hot water and some acetic acid and dissolved with hot water. The dye bath receives an addition of 0.5 g. of the product of 50 moles ethylene oxide on 1 mole oleyl alcohol and cold water is added to make up 500 ml. The pH of the dye (iii); a

in which A represents the remaining members necessary to form a or 6-membered heterocyclic ring with Ra Ra said heterocyclic ring selected from the group consisting of indoline, benz-(c,d)-indole, quinoxalone, quinazolone, 3-methyl-dihydro-(2,3)-benzthiazole, 3- ethyl-dihydro-(2,3)-benzthiazole, 3 ethyl-4,5-benzodihydro-(2,3)benzthiazole, 3,4 dirnethyl dihydro- (2,3)thiazole, 3 methyl-dihydro-(2,3)-benzoxazole, 1,6-dimethyl-dihydro-(1,2)-quinoline and 1 methyldihydro-( 1,4)-quinoline;

R is aryl selected from the group consisting of phenyl; 2-, 3- or 4-methylphenyl; 2-, 3- or 4-ethylphenyl; 4-isopropylphenyl; 4 tert. butylphenyl; 4- cyclohexylphenyl; 4-bisphenylyl; phenyl 4,5 tetramethylene; 2-, 3- or 4-chlorophenyl; 2,4-dichloro phenyl; 2-, 3- and 4-bromophenyl; 4-fiuorophenyl; 4- trifiuorophenyl; 4-acetylphenyl; 4-cyanophenyl; 4- methoxycarbonylphenyl; 4-ethoxycarbonylphenyl; 4- methylsulfonylaminophenyl; 3-methylsulfonylphenyl; 2-, 3- or 4-methoxyphenyl; 2-, 3- or 4-ethoxyphenyl; 4-isopropoxyphenyl; 4-methylmercaptophenyl; naphthyl-l; thienyl-2; furyl-2; pyridyl-Z; benzoxazolyl-Z; or benzthiazolyl-Z;

R R R R R and R independently of each other, are hydrogen; alkyl, alkyloxy, alkylthio, alkylamino, alkoxycarbonyl, alkylcarbonyl, alkylcarbonyloxy, alkylcarbonylamino or dialkylamino, in which the alkyl group contains 1-5 carbon atoms; beta cyanethyl; beta chloroethyl; beta methoxyethyl; beta ethoxyethyl; beta ethoxycarbonylethyl; aryl, aryloxy, arylalkyl in which the alkyl contains 1-5 carbon atoms, arylcarbonyloxy, arylcarbonyl, arylcarbonylamino, or arylthio, in which aryl is as defined above; cyclohexyl; hydroxy; amidocarbonyl; nitrile; nitro; amino; sulfonyl; mercapto; fluorine; chlorine; or bromine;

R is hydrogen or CN;

R is hydrogen; alkyl of l-5 carbon atoms; beta cyanethyl; allyl; beta chloroethyl; beta methoxyethyl; beta ethoxyethyl; beta ethoxycarbonylethyl; cyclohexyl; or aryl or arylalkyl in which the alkyl group contains 1-5 carbon atoms in which aryl is as defined above;

X is an anion;

m, n and p independently are the numbers 0 or 1 on the 2. The compound of claim 1 of the formula CHa CHz-CH: 01

3. The compound of claim 1 of the formula GHQO-CO CH CHa-CH1 01 4. The compound of claim 1 of the formula oHa 5. The compound of claim 1 of the formula 6. The compound of claim 1 of the formula CR -CH 7. The dye of claim 1 in which p is 1. 8. Dye of claim 1 having the formula CH CH; Cu

wherein R R and X are as defined in claim 1; R is lower alkyl; and in which the carbocyclic ring Y can contain the non-ionic substituents defined for R and R 9. Dye of the formula CHa Y3 1km 27 2-, 3- or 4-methoxyphenyl; 2-, 3- or 4-ethoxyphenyl; 4-isopropoxyphenyl; 4-methy1mercaptophenyl; naphthyl-l; thienyl-Z; furyl-2; pyridyl-Z; benzoxazolyl-Z; or benzthiazolyl-Z;

R is lower alkyl;

X is an anion;

R and R independently of one another are hydrogen or non-ionic substituents;

Y, Y Y and Y are hydrogen or one or two of Y, Y Y and Y are non-ionic substituents or Y and Y Y and Y or Y and Y taken together may form a fused benzo ring; said non-ionic substituents selected from the group consisting of alkyl, alkyloxy, alkylthio, alkylamino, alkoxycarbonyl, alkylcarbonyl, alkylcarbonyloxy, alkylcarbonylamino or dialkylamino in which the alkyl group contains 1-5 carbon atoms; beta cyanethyl; beta chloroethyl; beta methoxyethyl; beta ethoxyethyl; beta ethoxycarbonylethyl; aryl, aryloxy, arylalkyl in which the alkyl contains 1-5 carbon atoms, arylcarbonyloxy, arylcarbonyl, arylcarbonylamino, or arylthio in which aryl is as defined above; cyclohexyl; hydroxy; amidocarbonyl;

nitrile; nitro; amino; sulfonyl; mercapto; fluorine; chlorine; and bromine.

References Cited UNITED OTHER REFERENCES Wiley et al.: Pyrazoles, Pyrazolines, Pyrazolidines, Indazoles and Condensed Rings, pp. 221-222, Interscience Publishers (1967).

JOHN D. RANDOLPH, Primary Examiner U.S. Cl. X.R.

862, 177 R, 179; 260240 E, 240.1, 244 R, 278, 279 R, 288 R, 296 R, 306.8 F, 307 D, 309.2, 310 D, 319.1, 340.6, 

